Gasoline fuel composition



United States Patent Ofitice F EL CGMPOSITIGN South Euclid, and John 8.Mann, Warrensville Heigh Ohio, assignors to The Standard Oil'Com'pany,Cleveland, Ohio, ,a corporation of Ohio I No Drawing. Filed Mar. 15,1965, vSer.- No. 439,993

' 7 Claims. (Cl. 44-63) GASOLINE Richard J. DeGray,

The present invention relates 'to an improved gasoline and to the methodof its manufacture and more particularly pertains to a high octanegasoline containing tetraalkyl lead and a reaction product of an amideand a monocarboxylic acid or its anhydride or acid halide as leadappreciator and to the process for manufacture thereof. The presentinvention deals with a novel class of gasoline additives which increasethe octane number of leaded motor fuels. These additives, or tetra-alkyllead extenders asthey are sometimes referred to, consist of gasolinesoluble reaction products of a monocarboxylic acid or its anhydride withan amide having the grouping The additivesmost useful in the thefollowing:

present invention include O RPNJLMLW ing from 1 to 12 carbon .atoms.More preferred in the. Q

present invention are compounds of the foregoing types wherein R is analkyl group having'from 1 to 18 carbon atoms, R and R are eachindependently hydrogen or an alkylgroup containing from l to 4 carbonatoms, R is an alkyl or .alkenyl group having from -1 to 6 carbon atoms,R is an alkyl or alkenyl group containing from 1 to 18 carbon atoms, Ris an 'al-kylene group havingfrom 1 to 6 carbon atoms, R is an alkyl.group having from 1 to 12 carbon atoms and R- is an alkylene grouphaving from 1 to 12 carbon atoms. Specific compounds of the foregoingtypes which are particularly preferred in the present invention include:

" 'fuel, with 3,377,148 Patented Apr. v9.,

CH: CH:

In the foregoing compounds the exact structure of the acid adducts withthe various amides is unknown, The acid adducts are prepared by mixingthe carboxylic acid and the amide. The acetylated amides are prepared byreacting the amide which contains at least one hydrogen bonded to theamide nitrogen with the carboxylic acid anhydride or acyl halide. I V vV The effective concentration of the additives of this invention inleaded motor fuel range from about (X05 to about 3% by Weight based onthe weight of the motor maximum benefits being derived in therange offrom about 0.5 to 1.5% by Weight of the additive.

3 The increase in octane number obtained with the additives of thisinvention in a given gasoline varies'with' the con: centration of theadditive, the concentration of tetraethyl lead in the gasoline as wellas the type of fuel employed. Maximum response to the additives isobtained in an aromatic fuel. The additives also are generally moreeffective with increased concentration of the tetraalkyl lead in thegasoline. The amount of tetraalkyl lead in the gasolines useful in thepresent invention can vary from 1 to 6 ml. of tetraalkyl lead per gallonof gasoline.

The acid adduct additives of this invention may be prepared at moderatetemperatures, i.e., at room temperature or slightly above, by simplymixing the amide with the acid. The reactants are generally miscible andnormally a solvent is not necessary for carrying out the reaction. Ifdesired, the reaction may be carried out in the presence of a solventsuch as toluene or a catalytically reformed hydrocarbon, particularly ininstances in which one of the reactants is a solid. Generally theformation of the carboxylic acid-amide adduct is exothermic.

As was indicated earlier, the exact nature of the carboxylic acid-amide.adducts is not known but they are probably combined by primary orsecondary chemical bonding or by a combination of these two types ofbonds.

The reaction product of amides containing at least one hydrogen on theamide nitrogen with carboxylic acid or acyl halides are believed to beacylated amides.

This invention is further illustrated in the following example.

EXAMPLE The additives used were prepared as follows: (A) N-dodecyltrimethylene urea-acetic acid adduct,

glacial acetic acid. Upon shaking the mixture there was a definiteevolution of heat. Similar results were obtained when the foregoingreaction was carried out in the abr sence of toluene.

(B) Pyrrolidone-acetic acid adduct was prepared by mixing 17.02 g. ofpyrrolidone and 12.01 g. of glacial acetic acid at a temperatureslightly above 25 C. (the melting point of pyrrolidone). The heat ofreaction increased the temperature of the mixture and the resultingsolution was a homogeneous liquid.

(C) Pyrrolidone-acetic acid adduct was prepared as in B except that18.72 g. of pyrrolidone were reacted with 12.01 g. of acetic acid.

(D) N-methyl pyrrolidone-acetic acid adduct was prepared by mixing 19.82'g. of N-methyl pyrrolidone and 12.01 g. of glacial acetic acid withstirring at about room temperature. Heat was evolved from the reactionand the final solution was a homogeneous product.

=(E) 'N-methyl pyrrolidone-acetic acid adduct was prepared as in ,Dexcept that 20.80 g. of N-methyl pyrrolidone were reacted with 12.01 g.of glacial acetic acid.

(F) N-oleyl trimethylene urea-acetic acid adduct was prepared by aprocedure similar to that given in A using 80.4 g. of oleyl amine and12.01 g. of urea. To this reaction mixture were added 12.01 g. of aceticacid.

(G) Acetylated pyrrolidone was prepared by mixing 34.04 g. ofpyrrolidone and 20.42 g. of acetic anhydride in a 250 ml. flask. Themixture was heated to 110 C. and this was accompanied by a gradualchange in color of the reaction mixture to a dark brown color. At 160 C.the reaction appeared to be complete. The product was homogeneous andsoluble in gasoline.

(H) Pyrrolidone-acrylic acid adduct was prepared by mixing 85.10 g. ofpyrrolidone and 72.06 g. of acrylic acid with stirring. A considerableamount of heat was evolved. The product was a homogeneous liquid at roomtemperature.

The properties of the fuels (1-3) used are as follows:

ASTM D86 (Distillation Test) Properties 01 Fuel 2 Percent F.

Percent. saturates, 70 10 141 Percent Olefins, 8 30 202 PercentAromatics, 23 238 Reid Vapor Pressure, p.s i 9 70 272 Gravity at R,0.7388..... 90 344 Tetraethyl Lead, ce./gal., 2.58 394 ASTM D-86Properties of Fuel 3 Percent F.

Percent Saturates, 40- 10 168 Percent Olefins, 17.... 30 218 PercentAromatics, 43 40 258 Reid Vapor Pressure, p.s.i., 4.39 300 Gravity at 60R, 0.7872 90 366 Tetraethyl Lead, cc.lgal., 3.05 430 1 End Point.

Engine data illustrating the lead appreciator response obtained usingthe standard F-l and F-2 octane test procedures are shown in Tables I,II, III and IV. The additive compositions, additive concentrations andtetraethyl lead concentrations were varied and the results were comparedwith tertiary butyl acetate at its most effective concentration.

TABLE I.'.F1 OCTANE RESPONSE Lead Level, ccJgal 0 Additive B H G B H G BH G Coneenration:

Blank. 93. 1 97. 1 98. 7 98. 9 98. 7 0.25%. +1. 0 +0. 7 +1. 5 0.50% +1.5 +1. 1. +1. 0 0.75% +0. 1 +0. 1 +0. 1 +0. 7 +0. 6 +1. 1 +2.4 +1. 5 +1.4 1.00%. +2. 0 +1. 4 +1. 7 1.25, 0... +0. 2 +0. 3 +0. 3 0 -0. 2 +0. 7+1. 4 +1. 0 +2. 0 1.50%- +1. 3 +0. 8 +2. 2 1.75% +0. 6 +0. 4 +0. 6 0. 30. 7 +0. 5 +0. 8 +0. 4 +1. 7 0.75% t-Butyl Acetate +0. 1 +0. 5 +0.8 +0.6 +0. 9

Fuel: No. 3.

3,377,148 6 U v r TABLE irl-r-z OCTANE RESPONSE Lead Level, eta/gal 01.5 3.0 Additive B H G B H o B n 0 Concentration:

Blank 81. 1 86.8 87.3 7.8 87.5 0.25 +1.0 +0.7 +1.0 0.50 +1. 0 +1.2 +0.80.75 0 +0. 1 +0. 1 +0. 2 0 +0. 0 +1. 0 +1.7 +1.8 1.00 l +1.7 +1.8 +1.71.25 +0.5 +0.4 +0.2 --0.2 0.0 +0.4 +1.8 +1.2 +1.8 1.50 +1.1 +0.8 +1. 71.75% +0.5 +0.5 +0.0 0.3 -0.0 0.1 +1.0 +0.0 +1.8 0.75%i-nut lAeem;.-;;QL; +0.2 +0.1 +1.3 +1.-0 +1.2

Fuel: No. 3.

At the 3 cc. lead level, the additives of this invention exhibit theirmost favorable response, which in some cases is double the increasealforded by tertiary butyl acetate.

The optimum concentration for the reaction products pf pyrrolidone withacetic acid and acrylic acid was found in'the regionof from 0.5 to 1.5-weight percent. -With the -acetyl pyrrolidone, however, a peak in theresponse curve appeared at about 0.25% concentration at the 3 cc.tetraethyl lead level. i

The effect on octane number of reaction products of acetic acid withacetamide and the product 0 R-i'k-N-RLCHgOOOH I 1 wherein R is an alkylgroup having from-8m 10 carbon atoms, and R and R are methyl groups areshown in Ta-bIeIIII." These "data'i'ndicate that considerable increasein octane number in both the F-1 and F-2 ratings is obtained'with'theseadditives.

TABLE III Fu el: No. 1 plus 3.5'cc. tetramethyl lead per gal.

The gasoline samples listed in Table V were stored for ten days in thepresence of 1% Water before octanes were evaluated. (Continuously.during this. storage period the bottles containing the samples wereagitated in a manner l'which insured intimate contact between water andgaso- Table VI summarizes the road octane performance ofpyrrolidone-acetic acid, pyrrolidone-acrylic acid and ter tiary butylacetate as tetraethyl lead appreciatorsRatings were made in anall-weather chassis dynamometer room at 60 F. and relative humidity.Each fuel was rated three times in each ofjthree cars. Cars used werethe i961 Pontiac, 1961 Oldsmobile and 1962 Chrysler. At the 3 cc;tetraethyl lead level, the pyrrolidone acetate and acrylate were againdemonstrated to be superior to tertiary butyl acetate. An increase of0.1 octane was obtained with tertiary butyl acetate compared with 0.4and 0.6 increase for pyrrolidone-acetic acid and pyrrolidorie-acrylicacid, re- Pt Y-.

TABLE VL-ROAD OCTANE PERFORMANCE OF LEAD APPRECIATORS F-l F-2 OctaneOctane [F Fuel N0 2] I 4 Number Number Vol. Percent Add Tetraethyl LeadLevel, Blank (Fuel No. a plus 3 cc. tetraethyl lead)- 98. Y 87. 2 i t0.75% Dimethyl Acetamide-Aeetic Acid 100.3 V 89.8 I

100.5 0 CH: 100 8 C H11ClII-CHiCOOH 90.0 88.8 0

100. 5 101.1 The octane response of the reaction products of N-oleyl 45and N-dodecyl derivatives of trimethylene urea with 100 8 acetic acidare shown in Table IV.

TABLE IV.-OCTANE RESULTS F-i F-2 Fuel Treatments Octane A Octane OctaneA Octane Number Number Number Number Blank (Fuel No. 1 plus 3.5 cc.Tetraethyl Lead per gal.) 101. l 92. 5 1.00% Additive A 101.7 +0.6 92. 4-0. 1 Blank (Fuel No. 1 plus 3.2 cc. Tetraethyl Lead per gal.) 101. 4 97 0.5% Additive 101.8 +0. 4 92.8 +0. 1 1.0% Additive F 102.0 +0. 6 93. 1+0. 4

The eflect of N-methyl pyrrolidone-acetic acid adduct We claim:

and related compounds are disclosed in Table V. It is interesting tonote that pyrrolidone itself at 1% by weight concentration shows asignificant increase of 0.4 octane, but the effect is not as great asthat shown by the acetic acid reaction product with pyrrolidone. Theaddition of excess pyrrolidone to the acetic acid reaction product ofpyrrolidone results in no additional increase in octane 65 number.

TABLE V.OCIANE DATA F-i Fuel Treatments Octane A Octane Number NumberBlank 100. 8 1.0% Additive B-. 101.5 +0.7 1.0% Additive 0-.-. 101.5 +0.71.0 yrrolidone. 101. 2 +0. 4 1.0% 'tive 1)-- 101.4 +0.6 1.0% Additive E101. 3 +0. 5

1. A gasoline containing from 1 to 6 ml. of tetraalkyl lead per gallonand from 0.05 to 3% by weight of a lead appreciator selected from thegroup consisting of:

.1 "iL niLw is a hydrocarbon group is a hydrocarbon 5 grouphaving from 1to 18 carbon atoms, R is a hydrocarbondiradical having from 1- to12-carbons,- R is a- I member from the group consistingtof hydrogen anda hydrocarbon group having from 1 to 12 carbon atoms andR'l is ahydrocarbon diradical'having from 1 to 12 carbon atoms. 1

2. The gasoline of claim 1 wherein the lead appreciator V. I CnHu-NNH-CH'QCOOH CH1 CH2 C 1 3. The gasoline of claim 1 wherein the leadappreciator is Ca N-H-CHaC O OH HF- H1 4. The gasoline of claim 1wherein the lead appreciator is 0 II o 7 C 1 NfCB 'QBfl Hr- H:

'5. The gasoline of claim wherein the lead appreciator V GCHa(CH2)vCH=CH(CHa)1-N N-H-CHaC00H CID H H:

i i 6. The gasolineof claim l wherein the leadappreciator is V V W i I v7. The gasoline of claim 1 wherein the lead appreciator 1S 1 ReferencesCited DANIEL EIWYMAN, Primary Examiner.

Y. H. SMITH, Assistant Examiner.

1. A GASOLINE CONTAINING FROM 1 TO 6 ML. OF TETRAALKYL LEAD PER GALLONAND FROM 0.05 TO 3% BY WEIGHT OF A LEAD APPRECIATOR SELECTED FROM THEGROUP CONSISTING OF